Carbon nanotube product manufacturing system and method of manufacture thereof

ABSTRACT

A method of manufacturing a carbon nanotube product comprising: blending an unaligned carbon nanotube material with solid solvent particles; activating a nanotube solvent by liquefying the solid solvent particles; producing a nanotube dope solution by mixing the nanotube solvent and the unaligned carbon nanotube material; forming a carbon nanotube proto-product by extruding the nanotube dope solution; and forming an aligned carbon nanotube product by solidifying the carbon nanotube proto-product.

TECHNICAL FIELD

An embodiment of the present invention relates generally to a system andmethod for manufacturing a carbon nanotube product.

BACKGROUND

Production of articles from carbon nanotube molecules has foundapplication in numerous fields of technology. In particular, researchand development in production of carbon nanotube fibers and sheets havetaken a myriad of different directions. However, the availability ofconsistently producible high quality carbon nanotube articles has becomea concern for that desire to take advantage of the properties of thecarbon nanotube articles.

Thus, a need still remains for a system for manufacturing high qualitycarbon nanotube articles. In view of the ever-increasing commercialcompetitive pressures, along with growing consumer expectations and thediminishing opportunities for meaningful product differentiation in themarketplace, it is increasingly critical that answers be found to theseproblems. Additionally, the need to reduce costs, improve efficienciesand performance, and meet competitive pressures adds an even greaterurgency to the critical necessity for finding answers to these problems.

Solutions to these problems have been long sought but prior developmentshave not taught or suggested any solutions and, thus, solutions to theseproblems have long eluded those skilled in the art.

SUMMARY

An embodiment of the present invention provides a method of manufactureof a carbon nanotube product including: blending an unaligned carbonnanotube material with solid solvent particles; activating a nanotubesolvent by liquefying the solid solvent particles; producing a nanotubedope solution by mixing the nanotube solvent and the unaligned carbonnanotube material; forming a carbon nanotube proto-product by extrudingthe nanotube dope solution; and forming an aligned carbon nanotubeproduct by solidifying the carbon nanotube proto-product.

An embodiment of the present invention provides a method of manufactureof a carbon nanotube product including mixing an unaligned carbonnanotube material with a solvent precursor material; activating ananotube solvent by reacting the solvent precursor with a solventactivation agent; producing a nanotube dope solution by mixing thenanotube solvent and the unaligned carbon nanotube material; forming acarbon nanotube proto-product by extruding the nanotube dope solution;and forming an aligned carbon nanotube product by solidifying the carbonnanotube proto-product.

An embodiment of the present invention provides a carbon nanotubeproduct manufacturing system including: a solid state blending unitconfigured to blend an unaligned carbon nanotube material with solidsolvent particles; a homogenization unit configured to: activate ananotube solvent by liquefying the solid solvent particles; mix thenanotube solvent and the unaligned carbon nanotube material to produce ananotube dope solution; an extrusion assembly configured to extrude thenanotube dope solution as a carbon nanotube proto-product; and asolidification module configured to solidify the carbon nanotubeproto-product as an aligned carbon nanotube product.

Certain embodiments of the invention have other steps or elements inaddition to or in place of those mentioned above. The steps or elementswill become apparent to those skilled in the art from a reading of thefollowing detailed description when taken with reference to theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram for a carbon nanotube productmanufacturing system.

FIG. 2 is a schematic view of the mixing module for the carbon nanotubeproduct manufacturing system of FIG. 1.

FIG. 3 is a schematic view of the extrusion module of the carbonnanotube product manufacturing system of FIG. 1.

FIG. 4 is a schematic view of the solidification module of the carbonnanotube product manufacturing system of FIG. 1.

FIG. 5 is a schematic view of the post-production module of the carbonnanotube product manufacturing system of FIG. 1.

FIG. 6 is a flowchart for a method of manufacture of the aligned carbonnanotube product 102 of FIG. 1 by the carbon nanotube productmanufacturing system of FIG. 1.

DETAILED DESCRIPTION

The present invention generally relates to systems, methods, andapparatus, for processing of unaligned carbon nanotube materials. Oneaspect relates to a system for producing aligned carbon nanotubematerials in various forms. The system as disclosed herein includesmodular units, assemblies, devices, and the like for manufacture of thealigned carbon nanotube materials.

The following embodiments are described in sufficient detail to enablethose skilled in the art to make and use the invention. It is to beunderstood that other embodiments would be evident based on the presentdisclosure, and that system, process, or mechanical changes may be madewithout departing from the scope of an embodiment of the presentinvention.

In the following description, numerous specific details are given toprovide a thorough understanding of the invention. However, it will beapparent that the invention may be practiced without these specificdetails. In order to avoid obscuring an embodiment of the presentinvention, some well-known circuits, system configurations, and processsteps are not disclosed in detail.

The drawings showing embodiments of the system are semi-diagrammatic,and not to scale and, particularly, some of the dimensions are for theclarity of presentation and are shown exaggerated in the drawingfigures. Similarly, although the views in the drawings for ease ofdescription generally show similar orientations, this depiction in thefigures is arbitrary for the most part. Generally, the invention can beoperated in any orientation.

For convenience, certain terms employed in the entire application arecollected here. Unless defined otherwise, all technical and scientificterms used herein have the same meaning as commonly understood by one ofordinary skill in the art to which this invention belongs.

The term “substantially pure”, with respect to a carbon nanotubematerial, refers to a carbon nanotube material that is at least about75%, preferably at least about 85%, more preferably at least about 90%,and most preferably at least about 95% pure, with respect to carbonnanotube molecules making up the carbon nanotube material. Recast, theterms “substantially pure” or “essentially purified”, with regard to acarbon nanotube material, refers to a carbon nanotube material thatcontain fewer than about 20%, more preferably fewer than about 15%, 10%,8%, 7%, most preferably fewer than about 5%, 4%, 3%, 2%, 1%, or lessthan 1%, of molecules which are not of the desired carbon nanotubematerial.

As used herein the term “comprising” or “comprises” is used in referenceto compositions, methods, and respective component(s) thereof, that areessential to the invention, yet open to the inclusion of unspecifiedelements, whether essential or not. By way of further example, acomposition that comprises elements A and B also encompasses acomposition consisting of A, B and C. The terms “comprising” means“including principally, but not necessary solely”. Furthermore,variation of the word “comprising”, such as “comprise” and “comprises”,have correspondingly varied meanings. The term “consisting essentially”means “including principally, but not necessary solely at least one”,and as such, is intended to mean a “selection of one or more, and in anycombination.” In the context of the specification, the term “comprising”means “including principally, but not necessary solely”.

As used herein the term “consisting essentially of” refers to thoseelements required for a given embodiment. The term permits the presenceof additional elements that do not materially affect the basic and novelor functional characteristic(s) of that embodiment of the invention.

The term “consisting of” refers to compositions, methods, and respectivecomponents thereof as described herein, which are exclusive of anyelement not recited in that description of the embodiment.

As used in this specification and the appended claims, the singularforms “a,” “an,” and “the” include plural references unless the contextclearly dictates otherwise. Thus for example, references to “the method”includes one or more methods, and/or steps of the type described hereinand/or which will become apparent to those persons skilled in the artupon reading this disclosure and so forth.

It is understood that the foregoing detailed description and thefollowing examples are illustrative only and are not to be taken aslimitations upon the scope of the invention. Various changes andmodifications to the disclosed embodiments, which will be apparent tothose of skill in the art, may be made without departing from the spiritand scope of the present invention.

It should be understood that this invention is not limited to theparticular methodology, protocols, and reagents, etc., described hereinand as such can vary. The terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to limit thescope of the present invention, which is defined solely by the claims.

Referring now to FIG. 1, therein is shown a schematic diagram for acarbon nanotube product manufacturing system 100. The carbon nanotubeproduct manufacturing system 100 can produce an aligned carbon nanotubeproduct 102 from an unaligned carbon nanotube material 104. Theunaligned carbon nanotube material 104 is a structure containing amultitude of carbon nanotube molecules 106. For example, the unalignedcarbon nanotube material 104 can be a bulk solid fibrous structure of alow density. The carbon nanotube molecules 106 are the individual carbonnanotube macro molecules within the unaligned carbon nanotube material104 and the aligned carbon nanotube product 102. As an example, thecarbon nanotube molecules 106 can be single walled carbon nanotubemolecules, although it is understood that the carbon nanotube molecules106 can be of other structures, shapes or morphologies, such as doublewalled, multi-walled carbon nanotube molecules, or a combinationthereof. In the unaligned carbon nanotube material 104, the carbonnanotube molecules 106 can be randomly oriented and held together byattractive intermolecular van-der-Waals forces.

The aligned carbon nanotube product 102 is a material formed by aligningthe carbon nanotube molecules 106 axially, longitudinally, along thelong axis or a combination thereof of the lengths of the carbon nanotubemolecules 106. In general, the aligned carbon nanotube product 102 canbe produced by separating each of the carbon nanotube molecules 106 fromone another by overcoming the attractive intermolecular van-der-Waalsforces and reestablishing the attractive intermolecular forces in alengthwise orientation, which provides the basis for the highlydesirable mechanical properties. The aligned carbon nanotube product 102can be produced in a number of different forms. For example, the alignedcarbon nanotube product 102 can be in the form of filaments, fibers,films, or a combination thereof that can be assembled or integrated intoother materials or structures, such as threads, yarns, sheets, fabricsfoams, or tapes. The aligned carbon nanotube product 102 can be combinedwith itself or with other types of materials.

The carbon nanotube molecules 106 chosen for producing the alignedcarbon nanotube product 102 can be characterized by an aspect ratio oflength to diameter (L/D) and a purity determined by a G-band to D-band(G/D) ratio. For example, the carbon nanotube molecules 106 canpreferably have the aspect ratio greater than 500 and a G/D ratiogreater than 4, more preferably the carbon nanotube molecules 106 canhave an aspect ratio greater than 1000 and a G/D ratio greater than 6,most preferably the carbon nanotube molecules 106 can have an aspectratio greater than 2000 and a G/D ratio greater than 10.

The carbon nanotube product manufacturing system 100 can include one ormore processing modules to produce the aligned carbon nanotube product102. Each of the processing modules can include one or more physicalprocessing units, such as devices, machines, mechanisms, assemblies,physical coupling implements, or a combination thereof for manufacturingthe aligned carbon nanotube product 102. Examples of the units of thecarbon nanotube product manufacturing system 100 can include a mixingmodule 110, an extrusion module 120, a solidification module 130, a postproduction module 140, or a combination thereof. As a further example,the extrusion module 120 can be coupled to the homogenization unit 220,the solidification module 130 can be coupled to the extrusion module130, and the post production module 140 can be coupled to thesolidification module 130. In yet a further example, the modules can bean integrated in-line continuous or semi-continuous process.

The mixing module 110 is for producing a solution of the carbon nanotubemolecules 106 capable of being extruded. For example, the mixing module110 can include processing units to produce a nanotube dope solution 112from the unaligned carbon nanotube material 104. The nanotube dopesolution 112 is a liquid solution in which the carbon nanotube molecules106 have been separated from one another in a solvent. In someembodiments, the mixing module 110 can include units for solid stateblending of the unaligned carbon nanotube material 104, dissolution andliquid state mixing of the unaligned carbon nanotube material 104, or acombination thereof. In some embodiments, the mixing module 110 caninclude units for adjusting the concentration of the nanotube dopesolution 112. The details for the mixing module 110 will be discussedfurther below.

The extrusion module 120 is for processing the nanotube dope solution112 to form a carbon nanotube proto-product 122. For example, theextrusion module 120 is for homogenizing the temperature, pressure,chemical composition, or a combination thereof of the nanotube dopesolution 112 prior to formation of the carbon nanotube proto-product122. The carbon nanotube proto-product 122 is a material having theinitial physical form of the aligned carbon nanotube product 102 priorto full alignment of the carbon nanotube molecules 106. For example, thecarbon nanotube proto-product 112 can be produced by the extrusionmodule 120 having a composition that is primarily of solvent, asmeasured by volume or weight fraction. In some embodiments, theextrusion module 120 can include processing units to refine the nanotubedope solution 112, shape the nanotube dope solution 112 into variousphysical forms and shapes, or a combination thereof. The details for theextrusion module 120 will be discussed further below.

The solidification module 130 is for producing the aligned carbonnanotube product 102 from the carbon nanotube proto-product 122. In someembodiments, the solidification module 130 can include processing unitsto solidify the carbon nanotube proto-product 122, impart alignment tothe carbon nanotube molecules 106 within the carbon nanotubeproto-product 122, or a combination thereof. The details for thesolidification module 130 will be discussed further below.

The post production module 140 is for enhancing or modifying the alignedcarbon nanotube product 102. In some embodiments, the post-processingmodule 140 can include processing units for purification of the alignedcarbon nanotube product 102, optional modification of the aligned carbonnanotube product 102, manipulating or altering the physical form of thealigned carbon nanotube product 102, integration of the aligned carbonnanotube product 102 into additional structures or with additionalmaterials, or a combination thereof. The details for the post productionmodule 140 will be discussed further below.

In some embodiments, the carbon nanotube product manufacturing system100 can produce the aligned carbon nanotube product 102 as a carbonnanotube filament, fiber, or film. As an example, the aligned carbonnanotube product 102 in the form of the filament, fiber, or filmproduced by the carbon nanotube product manufacturing system 100 can becharacterized by one or more properties, such as tensile strength,elongation, stress fatigue, porosity or void fraction, molecularalignment, purity, electrical conductivity, or a combination thereof.The following are examples of properties of the aligned carbon nanotubeproduct 102 achieved through the carbon nanotube product manufacturingsystem 100.

The property of tensile strength for the aligned carbon nanotube product102 can be in excess of 3 GPa. In general, the tensile strength for thecarbon nanotube molecules 106 is approximately 60 GPa. The carbonnanotube product manufacturing system 100 can produce the aligned carbonnanotube product 102 that translates up to 40% of molecular-scaleproperties to the macroscale of the aligned carbon nanotube product 102,which can yield a CNT fiber with 24 GPa. For comparison, Kevlar standsat about 3.6 GPa, though many different grades of Kevlar are available.

The property of elongation for the aligned carbon nanotube product 102can be between 0.5% and 10% elongation until break. The carbon nanotubeproduct manufacturing system 100 can be tailored to trade-off betweenstrength and elongation such that the aligned carbon nanotube product102 can be stronger and stiffer at the expense of elongation, orvice-versa.

The property of stress fatigue for the aligned carbon nanotube product102 undergo billions of cycles of deformation until break at 15%deformation. The property of porosity or void fraction for the alignedcarbon nanotube product 102 can be at a void fraction of preferably lessthan 20%, more preferably less than 10%, and most preferably less than5% as determined by Brunauer-Emmett-Teller (BET) methods of nitrogen(N₂) or carbon dioxide (CO₂) gas absorption. The property of molecularalignment for the aligned carbon nanotube product 102 can be of a Hermanorientation factor in excess of preferably 0.8, more preferably 0.9 andmost preferably 0.95 as measured through diffraction or scatteringtechniques, such as X-ray and neutron diffraction. The property ofpurity for the aligned carbon nanotube product 102 can be a G/D ratiopreferably in excess of 5, more preferably in excess of 10 and mostpreferably in excess of 20, as measured by Raman spectroscopy. Theproperty of electrical conductivity for the aligned carbon nanotubeproduct 102 can be in excess of 10{circumflex over ( )}6 S/m.

The carbon nanotube product manufacturing system 100 can includeadditional units or devices to produce devices and components that canbe assembled with the aligned carbon nanotube product 102. For example,the devices and components assembled from the aligned carbon nanotubeproduct 102 can include wire antennas, patch antennas, coiltransformers, coaxial cables. In another example, the aligned carbonnanotube product 102 can be a component that is integrated into otherstructures, such as ropes, yarns, woven fabrics, resin pre-impregnatedtapes or fabrics, foams, chopped fiber filler material, or laminatedfilms.

Referring now to FIG. 2, therein is shown a schematic view of the mixingmodule 110 for the carbon nanotube product manufacturing system 100 ofFIG. 1. The mixing module 110 can include one or more processing unitsto produce the nanotube dope solution 112 from the unaligned carbonnanotube material 104. For example, the mixing module 110 can include ablending unit 202, a homogenization unit 220, a concentration adjustmentunit 230, or a combination thereof.

The blending unit 202 is for solid state comminuting, classification,blending, or a combination thereof of materials. More specifically, theblending unit 202 can produce a free-flowing dry powder blend materialthat will not spontaneously separate or segregate during transfer. Forexample, in one embodiment, the blending unit 202 can be configured touniformly disperse a nanotube solvent 204 as solid solvent particles 206throughout the unaligned carbon nanotube material 104 to produce a solidstate blend 208. In general, the since the nanotube solvent 204 issolidified into the solid solvent particles 206, the solid state blend208 of the solid solvent particles 206 and the unaligned carbon nanotubematerial 104 is a dry mixture. In another embodiment, the blending unit202 can be configured to uniformly disperse a solvent precursor material240 throughout the unaligned carbon nanotube material 104 to produce thesolid state blend 202. In a further embodiment, the blending unit 202can be configured to physically process the unaligned carbon nanotubematerial 104 without the addition of the nanotube solvent 204.

In one example, the nanotube solvent 204 is a solvent capable ofdissolution of the carbon nanotube molecules 106 in the unaligned carbonnanotube material 104. More specifically, the nanotube solvent 204 canbe capable of protonating the delocalized π electron on the sp2 carbonlattice of the carbon nanotube molecules 106. As an example, the carbonnanotube solvent 204 can be an acid, such as chlorosulfonic acid(HSO₃Cl), fluorosulfonic acid, fluorosulfuric acid, hydrochloric acid,methanesulfonic acid, nitric acid, hydrofluoric acid, fluoroantimonicacid, magic acid, or any other type of carborane-based acids. As anotherexample, the nanotube solvent 204 can be a supercritical fluid, which isa substance at a temperature and pressure above its critical point. Thenanotube solvent 204 as the supercritical fluid provides screening ofthe electrostatic interactions between solute molecules, in this casethe carbon nanotube molecules 106, to negate surface tension effects andparticle-particle interactions and enable solution processing as thenanotube dope solution 112 described herein. Past the critical point ofthe nanotube solvent 204, its temperature and pressure can be regulatedto maintain maximum solubility of the carbon nanotube molecules 106 suchthat the nanotube solvent 204 in the supercritical state can beconsidered athermal for all effective purposes. As an example, thenanotube solvent 204 as the super critical fluid can includesupercritical carbon dioxide.

The solvent precursor material 240 is a chemical compound that alone isincapable of dissolving the unaligned carbon nanotube material 104. Ingeneral, the solvent precursor material 240 is a solid material that canbe mixed with, reacted with, or a combination thereof of a solventactivation agent 242 to produce the nanotube solvent 204. An examplecombination of the solvent precursor material 240 and the solventactivation agent 242 can be phosphorous pentachloride in powder form andsulfuric acid, respectively.

In one embodiment, the blending unit 202 can include a blending chamber210 configured to receive and blend the unaligned carbon nanotubematerial 104 and the solid solvent particles 206. As an example, theblending chamber 210 can be a vessel having a conical shape. As aspecific example, the blending chamber 210 can include walls with anangle of repose between 45° and 75°, and most preferably 60°, tofacilitate discharge of the solid state blend 208. For illustrativepurposes, the blending chamber 210 is shown having a conical shape,although it is understood that the blending chamber 210 can be of othershapes or configurations, such as a cylindrical, ovular profile, or eggshape.

The blending unit 202 can include blending elements within the blendingchamber 210. For example, the blending elements can be a helical screwtravelling a path determined by the interior surface of the blendingchamber 210.

The blending elements can include separation instruments for physicalseparation of the unaligned carbon nanotube material 104. For example,the separation instruments can be small bristles, claws, or hooks. Theseparation instruments can be attached to or extend from the surface ofthe blending elements. For example, the blending elements can includethe separation instruments along their surface to pull apart theunaligned carbon nanotube material 104. In some embodiments, theblending elements can expose the surfaces of the unaligned carbonnanotube material 104 to the solid solvent particles 206. In otherembodiments, the blending elements can expose the surfaces of theunaligned carbon nanotube material 104 to the solvent precursor material240.

The blending unit 202 includes charging capability from the top andsides of the blending chamber 210. For example, the charging capabilityfor the unaligned carbon nanotube material 104 can include one or moremechanical feeder mechanisms.

In some embodiments, the charging capability of the blending unit 202for the nanotube solvent 204 in the liquid state can include one or morespray nozzles, mist nozzle, atomizers, or a combination thereof locatedat various positions within the blending unit 202. As a specificexample, spray nozzles or atomizers can be configured in such a way asto dispense the nanotube solvent 204 in a liquid form at a droplet sizeto promote formation the solid solvent particles 206 in the form ofamorphous or crystalline particles. In another embodiment, the chargingcapability into the blending unit 202 for the nanotube solvent 204 caninclude the capability of introducing the solid solvent particles 206 orthe solvent precursor material 240.

Examples of the solid charging capability can include powder dispensersor powder coating mechanisms. The blending unit 202 can include adischarge capability for the solid state blend 208 through the bottom ofthe blending unit 202.

The blending unit 202 can include a blend recirculation loop 218. Theblend recirculation loop 218 can be a closed recirculating loop aroundthe blending unit 202. The blend recirculation loop 218 enables theblending unit 202 to continuously recirculate the unaligned carbonnanotube material 104 through the blending unit 202.

The blending unit 202 can include a temperature control apparatus. Forexample, the temperature control apparatus can include an insulationlayer, a liquid nitrogen or liquid helium jacketed cooling system, or acombination thereof.

The blending unit 202 can be coupled to the homogenization unit 220. Thehomogenization unit 220 is for producing the nanotube dope solution 112.The homogenization unit 220 can be an apparatus or device that includesa mixing element within an enclosed mixing chamber 224, such as anenclosed reciprocating kneading assembly. As an example, thehomogenization unit 220 can be horizontally oriented with the mixingelement as a single screw or twin screw kneading assembly enclosed in abarrel. The mixing element can provide low-medium shear for mixing ofthe materials within the homogenization unit 220. The homogenizationunit 220 can be configured to allow interchangeability of the mixingelement and the enclosed mixing chamber 224.

In some embodiments, the homogenization unit 220 can include chargingcapabilities along the mixing chamber 224. In some embodiments, themixing chamber 224 can include spray heads or nozzles to introduce thesolvent activation agent 242 into the mixing chamber 224. In otherembodiments, the mixing chamber 224 can include spray heads or nozzlesto introduce the nanotube solvent 204 into the mixing chamber 224.

The enclosed mixing chamber 224 can include volatile gas removalcapabilities. In particular, the enclosed mixing chamber 224 canevacuate gas and other volatile by-products, such as hydrochloric acid(HCl) gas, produced during the dissolution of the unaligned carbonnanotube material 104 in the nanotube solvent 204, reaction of thesolvent precursor material 240 with the solvent activation agent 242, ora combination thereof.

The homogenization unit 220 can include temperature control capabilitiesto monitor, change, maintain, or a combination thereof the temperaturewithin the homogenization unit 220. For example, the homogenization unit220 can be capable of a gradual or incremental increase in temperatureover a given period of time. In some embodiments, the temperaturecontrol capability of the homogenization unit 220 can enable controlledliquefaction of the solid solvent particles 206 to the nanotube solvent204 in a liquid state. In other embodiments, the temperature controlcapability of the homogenization unit 220 can enable a gradual increasein temperature to control the reaction, mixing, or a combination thereofbetween the solvent precursor material 240 with the solvent activationagent 242.

Measurement units can be included at one or more positions along thehomogenization unit 220 to monitor the quality of the nanotube dopesolution 112. For example, the measurement units can be inline sensorunits, including spectrometers to measure the wavelength shift due tothe protonation of the carbon nanotube backbones. As another example,the measurement units can be devices for rheological evaluation of thenanotube dope solution 112. In another example, the measurement unitscan be devices for optical measurements of the birefringence of thenanotube dope solution 112.

The homogenization unit 220 can include a flow recirculation loop 226 toallow recirculate the nanotube dope solution 112 through thehomogenization unit 220. Additional mixing hardware, such as a highshear mixer, can be including along the flow recirculation loop 226.

The mixing module 110 can optionally include the concentrationadjustment unit 230, as indicated by the dashed outlined arrow. Theconcentration adjustment unit 230 is for adjusting the concentration ofthe nanotube dope solution 112. The concentration adjustment unit 230can include one or more of a pressure and temperature controlled vesselconfigured to remove or add specified amounts of the nanotube solvent204 from or to the nanotube dope solution 112. For example, theconcentration adjustment unit 230 can include one or more distillationcolumns or apparatus configured for evaporation of the nanotube solvent204 from the nanotube dope solution 112. For illustrative purposes, theconcentration adjustment unit 230 is shown with a single instance of thedistillation apparatus although it is understood that the concentrationadjustment unit 230 can include multiple instances of the distillationapparatus coupled to one another in parallel, series, or a combinationthereof to process the nanotube dope solution 112. In another example,the concentration adjustment unit 230 can include a concentrationrecirculation loop 232 to recirculate the nanotube dope solution 112through the concentration adjustment unit 230.

The concentration adjustment unit 230 can be configured to operate undervarious atmospheric conditions and compositions. For example, theconcentration adjustment unit 230 can provide an HCl saturatedatmosphere that can be co-fluxed with nanotube solvent 204 that hasevaporated from the nanotube dope solution 112. As another example, theconcentration adjustment unit 230 can be configured to operate under arange of pressures, temperatures, or a combination thereof. In general,the concentration adjustment unit 230 can be configured to operate atpressures of 30 to 35 mm Hg or 0.039 to 0.046 atmospheres andtemperatures ranging from 85 to 90° C.

The concentration adjustment unit 230 can include measurement devices tomonitor the concentration of the nanotube dope solution 112. Forexample, the measurement devices can include rheometers for contact ornon-contact evaluation of viscoelasticity and liquid crystallinityproperties of the nanotube dope solution 112. In another example, themeasurement devices can include spectrometers to determine thewavelength shift associated with the protonation of the backbones of thecarbon nanotube molecules 106 in the nanotube dope solution 112 by Ramanspectroscopy.

Referring now to FIG. 3, therein is shown a schematic view of theextrusion module 120 of the carbon nanotube product manufacturing system100 of FIG. 1. The extrusion module 120 can include one or moreprocessing units to produce the carbon nanotube proto-product 122 fromthe nanotube dope solution 112. For example, the extrusion module 120can include a flow drive mechanism 312, a filtration unit 302, anextrusion assembly 310, an extrusion flow manifold 316, or a combinationthereof.

The extrusion module 120 can be coupled to the mixing module 110 of FIG.2. For example, the extrusion module 120 can be coupled to the mixingmodule 110 by a fluid transfer path 350, such as a pipe or tube. Thenanotube dope solution 112 can be transferred through the fluid transferpath 350 from the mixing module 110 to the extrusion module 120. In someembodiments, the fluid transfer path 350 can include static mixingelements to create a sustained turbulent flow regime for the nanotubedope solution 112, which provides mixing and controlled heat transferfrom heat exchange fluid recirculation inside the static mixingelements, outside the static mixing elements, or a combination thereof.

The extrusion module 120 can receive the nanotube dope solution 112through the flow drive mechanism 312. The flow drive mechanism 312 isfor promoting flow of the nanotube dope solution 112 through theextrusion module 120 and maintaining homogenous properties of thenanotube dope solution 112. The flow drive mechanism 312 providesdevelopment of consistent pressure, which promotes uniform flow of thenanotube dope solution 112 through the extrusion module 120. As aspecific example, the flow drive mechanism 312 can be a twin-screwextruder which is capable of being “starve-fed” and provides a balanceof kneading and mixing elements, which assists in maintaining homogenousproperties such as temperature, pressure, concentration, or acombination thereof for the nanotube dope solution 112.

In some embodiments, the extrusion module 120 can include the filtrationunit 302. The filtration unit 302 can be included to increase the purityof the nanotube dope solution 112. For example, the filtration unit 302can include filtration elements 304 to remove residual particles, suchas metallic catalyst particles, amorphous carbon particles, sp3 carbonparticles, or a combination thereof from the nanotube dope solution 112.Different embodiments of the filtration unit 302 can include variousconfigurations and combinations of the filtration elements 304 dependingon the size of the residual particles or the purity of the unalignedcarbon nanotube material 104. For example, the filtration unit 302 caninclude one or more of a coarse filtration element 330, such as coarsescreen packs or coarse screen changers, one or more of a fine filtrationelement 332, such as fine screen packs or fine screen changers, or acombination thereof. The filtration elements 304 can be configured forcontinuous or semi-continuous renewal or changeable during operation ofthe filtration unit 302. In some embodiments, the filtration unit 302can include can include booster pumps and pressure sensors as needed toaid or promote flow of the nanotube dope solution 112 through thefiltration elements 304.

The extrusion flow manifold 316 can be coupled to the filtration unit302. The extrusion flow manifold 316 is for directing the flow of thenanotube dope solution 112 within the extrusion module 120. Morespecifically, any of the passages in the extrusion flow manifold 316that the nanotube dope solution 112 flows through prior to exiting theextrusion unit 120 can have adjustable construction to alter the patternor symmetry of flow of the nanotube dope solution 112 to achieve desiredresult after exit from the extrusion unit 120. The extrusion flowmanifold 316 can separate or merge the flow of the nanotube dopesolution 112 in various configurations to accommodate different flowschemes through the extrusion module 120. As one example, the extrusionflow manifold 316 can accommodate different schemes or arrangements ofthe filtration elements 304 of the filtration unit 302 in thefractionation unit 306, such as a recirculation loop (not shown) throughto recirculate the nanotube dope solution 112 through the filtrationunit 302.

The extrusion flow manifold 316 can include a fractionation pathway 306.The fractionation pathway 306 is for separation of the carbon nanotubemolecules 106 in the nanotube dope solution 112 based on the aspectratio of the carbon nanotube molecules 106. For example, thefractionation pathway 306 can include elements configured to impart asheering force on the flow of the nanotube dope solution 112. Undersufficiently high shear, it is expected that the nanotube dope solution112 will phase separate into a highly crystalline phase 332, which iscomprised primarily of the carbon nanotube molecules 106 having thehighest aspect ratio in the nanotube dope solution 112, and aconcentrated isotropic phase 330, which is comprised primarily of thecarbon nanotube molecules 106 having the lowest aspect ratio in thenanotube dope solution 112.

The extrusion flow manifold 316 can accommodate different schemes orarrangements of the flow for the different phases in the fractionationpathway 306. For example, the fractionation pathway 306 can include flowseparation and recombination manifold configured to separate andredirect the concentrated isotropic phase 330 from the highlycrystalline phase 332 as processing waste or low-grade material. Thehighly crystalline phase 332 can be allowed to proceed towards theextrusion assembly 310. Optionally, the extrusion flow manifold 316 caninclude pumps to drive the flow of the highly crystalline phase 332 andthe concentrated isotropic phase 330 through to the extrusion flowmanifold 316 to the extrusion assembly 310.

The extrusion assembly 310 is for producing the carbon nanotubeproto-product 122. The extrusion assembly 310 can include an extrusiondie 314. The extrusion die 314 is for extrusion of the nanotube dopesolution 112 to form the carbon nanotube proto-product 122. For example,the extrusion die 314 can be for shaping, initial alignment, or acombination thereof carbon nanotube proto-product 122. The extrusionassembly 310 can be configured to include one or more instances of theextrusion die 314. In general, the extrusion assembly 310 can includethe extrusion die 314 with a die opening or aperture corresponding tothe form factor of the carbon nanotube proto-product 122 and,ultimately, the aligned carbon nanotube product 102.

The extrusion die 314 for forming, shaping, and initial alignment of thecarbon nanotube proto-product 122 as a fiber or filament, or film can beset in one or more different configurations. In the case of producingthe carbon nanotube proto-product 122 in the form of a film, theextrusion die 314 can be a slotted die. In the case of producing thecarbon nanotube proto-product 112 in the form of a fiber or filament,the extrusion die 314 can be a single holed spinneret or multi-holedspinneret. In general, the hole in the extrusion die 314 can have aconical cross-sectional profile terminating in a flat land of lengthsuitable to elongate domains and promote alignment of the carbonnanotube molecules 106. As another example, the spinneret housing forthe extrusion die 314 can be static. In a further example, the spinnerethousing for the extrusion die 314 can be held inside a sealed bearingassembly, which allows for the twisting, rotation, or a combinationthereof of the liquid crystalline domains of the nanotube dope solution112 during flow to confer extra strength to the carbon nanotubeproto-product 122 once the domains are solidified in the twistedconfiguration, the spiral configuration, the helical configuration, or acombination thereof.

The extrusion assembly 310 can optionally include a vibratory apparatuscongruent with or upstream of the extrusion die 314. The vibrationsproduced by the vibratory apparatus can aid flow of the nanotube dopesolution 112 through the extrusion die 314 by disturbing undesiredelastic turbulence immediately prior to the outlet of the extrusion die314, improving flow stability by reducing undesirable frictional andshearing effects along flow surfaces, or a combination thereof.

The extrusion flow manifold 316 can accommodate inclusion of multipleinstances, various types, and geometries of the extrusion die 314, suchas for co-extrusion of the nanotube dope solution 112. In a furtherexample, the extrusion flow manifold 316 can accommodate different flowand production rates, as well as allow for the use of a plurality ofupstream and downstream components to increase production capacitywithout substantially altering the architecture of the system.

Referring now to FIG. 4, therein is shown a schematic view of thesolidification module 130 of the carbon nanotube product manufacturingsystem 100 of FIG. 1. The solidification module 130 can include one ormore processing units to produce the aligned carbon nanotube product 102from the carbon nanotube proto-product 122. For example, thesolidification module 130 can include an initial alignment unit 402, anirradiative coagulation unit 404, an intermediate alignment unit 408, achemical coagulation unit 410, a solid state alignment unit 414, or acombination thereof.

The initial alignment unit 402 is for imposing an alignment to thecarbon nanotube molecules 106 in the carbon nanotube proto-product 122after exit from the extrusion module 120. For example, the initialalignment unit 402 can be a temperature-controlled drum or Godet rollassembly. The initial alignment unit 402 can be configured to draw thecarbon nanotube proto-product 122 under tension at speed faster than theflow speed at the extrusion die 314 of FIG. 3 to impose alignment on thecarbon nanotube molecules 106 and draw down the cross-sectional area ofthe carbon nanotube proto-product 122.

The irradiative coagulation unit 404 is for irradiative solidificationof the carbon nanotube proto-product 122. For example, the irradiativecoagulation unit 404 can include a radiation source 406, such as anarray of infrared (IR) radiation emitters. The irradiative coagulationunit 404 can include the radiation source 406 arranged around theproto-product in a controlled atmosphere. The radiation emitted from theradiation source 406 can induce coagulation of the carbon nanotubeproto-product 122.

The radiation source 406 is capable of emitting radiation at awavelength such that absorption by the nanotube solvent 204 is minimizedand absorption by carbon nanotube molecules 106 of the carbon nanotubeproto-product 122 is maximized. The radiation source 406 can beconfigured to pulse the radiation to prevent localized heating effects.

The irradiative coagulation unit 404 can include devices to evacuatevolatile substances and impose gas flow on the atmosphere surroundingthe carbon nanotube proto-product 122. This provides convective heattransfer and assists in controlling the coagulation rate of the carbonnanotube proto-product 122, as well as aid in conveying the carbonnanotube proto-product 122.

The intermediate alignment unit 408 is for imparting alignment to thecarbon nanotube molecules 106 in the carbon nanotube proto-product 122in a partially solidified state. For example, the intermediate alignmentunit 408 can be a temperature-controlled drum or Godet roll assembly.The intermediate alignment unit 408 can be configured to draw the carbonnanotube proto-product 122 under tension at speed faster than the flowspeed at the extrusion die 314 to impose alignment on the carbonnanotube molecules 106. The rate and tension under which the carbonnanotube proto-product 122 is drawn by the intermediate alignment unit408 can be the same as, greater than, or less than that of the initialalignment unit 402.

The chemical coagulation unit 410 is for chemical solidification of thecarbon nanotube proto-product 122. The chemical coagulation unit 410 canexpose the carbon nanotube proto-product 122 to a chemical coagulant412. The chemical coagulant 412 is a chemical compound that is a solventfor the nanotube solvent 204 and a non-solvent for carbon nanotubeproto-product 122. For example, the chemical coagulant 412 can includeacetone, water, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), ether,chloroform, a mixture of sulfuric acid in water. As an example, theconcentration of the chemical coagulant 412 can be at a concentration ofless than 20%, a mixture of acetic acid in water at a concentration ofless than 40%, or a combination thereof.

For illustrative purposes, the chemical coagulant unit 410 isillustrated with a shower head or spray nozzle to apply the chemicalcoagulant 412 to the carbon nanotube proto-product 122, however it isunderstood that the chemical coagulant unit 410 can be in a differentconfiguration. For example, the carbon nanotube proto-product 122 caninclude a bath or immersion tank, a continuously renewed fluid film, ora combination thereof that exposes the carbon nanotube proto-product 122to the chemical coagulant 412. The chemical coagulation unit 410 can beconfigured to provide a homogeneous rate of coagulation along thecross-section of the carbon nanotube proto-product 122. The chemicalcoagulation unit 410 can include devices and mechanisms to provideatmospheric control, convective heat transfer within the chemicalcoagulation unit 410, such as through evacuation of the volatilesubstances, imposed gas flow on the atmosphere surrounding the carbonnanotube proto-product 122, and aid in conveying the carbon nanotubeproto-product 122.

The solid state alignment unit 414 is for imparting alignment to thecarbon nanotube molecules 106 in the carbon nanotube proto-product 122in a solidified state. For example, the solid state alignment unit 414can be a temperature-controlled drum or Godet roll assembly. Theintermediate alignment unit 408 can be configured to draw the carbonnanotube proto-product 122 under tension at speed faster than the flowspeed at the extrusion die to impose alignment on the carbon nanotubemolecules 106. Final dimensions of the aligned carbon nanotube product102 can be set by the solid state alignment unit 414. The rate andtension under which the carbon nanotube proto-product 122 is drawn bythe solid state alignment unit 414 can be the same as, greater than, orless than that of the initial alignment unit 402, the intermediatealignment unit 408, or a combination thereof. The solid state alignmentunit 414 can include a creel for uptake and storage of the alignedcarbon nanotube product 102.

Referring now to FIG. 5, therein is shown a schematic view of the postproduction module 140 of the carbon nanotube product manufacturingsystem 100 of FIG. 1. The post production module 140 can include one ormore processing units to modify the aligned carbon nanotube product 102.For example, the post production module 140 can include a purificationunit 502, a functionalization unit 512, a coating unit 514, a dopingunit 516, a product integration unit 518, or a combination thereof.

The purification unit 502 is for removing residual processing substancesfrom the aligned carbon nanotube product 102. For example, thepurification unit 502 can be configured to remove residual amounts ofthe nanotube solvent 204 of FIG. 2, the chemical coagulant 412 of FIG.4, other undesired residual particle on the aligned carbon nanotubeproduct 102, or a combination thereof. The purification unit 502 caninclude a solvent removal unit 504, a thermal annealing unit 506, achemical wash unit 508, or a combination thereof. The purification unit502 can be coupled directly or indirectly to the extrusion module 120 toreceive the aligned carbon nanotube product 102.

The solvent removal unit 504 is for removing residual traces of thenanotube solvent 204 from the aligned carbon nanotube product 102. Forexample, of the solvent removal unit 504 can include an aqueous bath,shower head, spray nozzle, or a combination thereof to wash the alignedcarbon nanotube product 102. The solvent removal unit 504 can beconfigured to deliver and maintain the aqueous wash in, for example, atemperature range of approximately 60° C. to 80° C.

The thermal annealing unit 506 is for removing residual traces of thechemical coagulant 412 from the aligned carbon nanotube product 102. Forexample, the thermal annealing unit 506 can include an oven or enclosedheating element configured to evacuate gases and volatile substancesfrom the environment around the aligned carbon nanotube product 102.

The chemical wash unit 508 is for removing residual traces of processby-product substances from the aligned carbon nanotube product 102. Forexample, the chemical wash unit 508 can include a spray nozzle, a showerhead, a bath or tank, a continuously renewed fluid film, or acombination thereof to expose the aligned carbon nanotube product 102 toa chemical wash solution. The choice of the chemical wash solution candepend on the choice of chemical coagulant 412 used in the chemicalcoagulation unit 410 of FIG. 4.

Optionally, the post production module 140 can include one or moreadditional units for further processing of the aligned carbon nanotubeproduct 102. For example, the post production module 140 can includeoptional units, such as the functionalization unit 512, the coating unit514, the doping unit 516, the product integration unit 518, or acombination thereof. In general, the inclusion of the optional units ofthe post production module 140, as indicated by the dashed lines andarrows, can depend on an intended application for the aligned carbonnanotube product 102.

The functionalization unit 512 is for modifying the molecular structureof the aligned carbon nanotube product 102. For example, thefunctionalization unit 512 can include a reaction chamber, an oven, or acombination thereof for covalent chemical functionalization of thealigned carbon nanotube product 102.

The coating unit 514 is for applying a coating substance on the alignedcarbon nanotube product 102. For example, the coating unit 514 caninclude an apparatus for mechanical coating of the of the aligned carbonnanotube product 102, such as a dip-coater, roll-to-roll coater,slide-coater, immersion coater, or a combination thereof. In anotherexample, the coating unit 514 can include an apparatus for electrolyticcoating of the of the aligned carbon nanotube product 102, such as anelectrolytic bath or tank containing an ionic compound for aqueousdispersion at a suitable zeta potential level. In a further example, thecoating unit 514 can include an apparatus capable of electrostaticcoating of charged solid particles or gas-phase deposition on thealigned carbon nanotube product 102.

The doping unit 516 is for non-covalent chemical functionalization ofthe aligned carbon nanotube product 102. The doping unit 516 can includea doping chamber with functionality and capabilities based on the dopingprocess. In one example, the doping unit 516 can include a vacuum ovenfor a gas phase doping process. In another example, the doping unit 516can include a spray nozzle, a shower head, a bath or tank, acontinuously renewed fluid film, or a combination thereof for a liquidphase doping process.

The product integration unit 518 is for integration of the alignedcarbon nanotube product 102 into devices, components, or structures. Asan example, the production integration unit 518 can include units ordevices to integrate one or more instances of the aligned carbonnanotube material 102 into a structure such as ropes, yarns, wovenfabrics, foams, resin pre-impregnated tapes or fabrics, chopped fiberfiller material, or laminated materials. Examples of such units caninclude looms, cradles, winders, presses, rollers, or laser cutters.Similarly, the product integration unit 518 can include units tointegrate the aligned carbon nanotube product 102 into devices orcomponents, which can include wire antennas, patch antennas, coiltransformers, coaxial cables, or a combination thereof.

Referring now to FIG. 6, therein is shown a flowchart for a method 600of manufacture of the aligned carbon nanotube product 102 of FIG. 1 bythe carbon nanotube product manufacturing system 100 of FIG. 1. Themethod 600 can include a number of steps to manufacture the alignedcarbon nanotube product 102. The following manufacturing steps and arearranged below for illustrative purposes, although it is understood thatthe steps can be arranged in other sequences or arrangements.

In an embodiment of the invention, the method 600 can include a materialpreparation step 602. The material preparation step 602 is for preparingmaterials to be processed by the carbon nanotube product manufacturingsystem 100. For example, in the material preparation step 602, thenanotube solvent 204 can be prepared for solid state blending with theunaligned carbon nanotube material 104.

In some embodiments, the nanotube solvent 204 can be provided in aliquid state to the blending chamber 210 of blending unit 202, both ofFIG. 2, and can be cooled to enable solid state blending of the nanotubesolvent 204 and the unaligned carbon nanotubes material 104. Morespecifically, sufficient cooling of the blending chamber 210 can benecessary to convert the nanotube solvent 204 from a liquid state to asolid state and maintain the dry solid state for the duration of theblending process. The forming of the solid solvent particles 206 duringblending can ensure that the initiation of reaction between nanotubesolvent 204 and the unaligned carbon nanotube material 104 is prevented.For example, prior to introduction of the nanotube solvent 214, thematerial preparation step 602 can include introducing a chamber coolantin a liquid or gaseous phase into the blending chamber 210 until a solidblending temperature is reached. As a specific example, the solidblending temperature is preferably less than 100° C. It is preferredthat chamber coolant is a chemically inert substance, such as nitrogen(N2) or helium (He). The chamber coolant can be introduced into theblending chamber 210 by a pressure differential directed along acontained pathway from a coolant reservoir into the blending chamber 210to cool and maintain the interior of the blending chamber 210 at thesolid blending temperature. Optionally, the unaligned carbon nanotubematerial 104 can be introduced to the blending unit 202 for cooling tothe solid blending temperature prior to introduction of the nanotubesolvent 204.

Prior to introducing the nanotube solvent 204 into the blending chamber210, the nanotube solvent 204 can be stored in a compartment orreservoir of the blending unit 202. Once the blending chamber 210 hasbeen prepared, such as after cooling to the solid blending temperature*, the method 600 can continue to a solid state blending step 606. Thesolid state blending step 606 is for dry solid state comminuting,classification, blending, or a combination thereof of materials. Morespecifically, a free-flowing powder blend material that will notspontaneously separate or segregate during transfer can be produced. Forexample, in the solid state blending step 606, the nanotube solvent 204in a dry solid state can be blended with the unaligned carbon nanotubematerial 104 to form the solid state blend 208 of FIG. 1 as a drymixture. In the solid state blending step 606, the unaligned carbonnanotube material 104 can be introduced to the blending chamber 210 ofthe blending unit 202. As an example, the unaligned carbon nanotubematerial 104 can be introduced into the blending chamber 210 at a rateto maintain a state of being “starve-fed”.

In one embodiment, the solid state blending step 606 can continue withthe introduction of the nanotube solvent 204 or the solvent precursormaterial 240 of FIG. 2 into the blending chamber 210. In oneimplementation of the solid state blending step 606, for the nanotubesolvent 204 provided in a liquid state, the nanotube solvent 204 can beintroduced into the blending chamber 210 in a way as to promote theformation of the solid solvent particles 206, and more specifically,amorphous or crystalline particles. Formation of the solid solventparticles 206 can be achieved through introducing the nanotube solvent204 at a sufficiently small droplet size to meet a cooling rate tofreeze the nanotube solvent 204. In this implementation, the unalignedcarbon nanotube material 104 can be cooled to the solid blendingtemperature prior to blending with the solid solvent particles 206.

The amount of the nanotube solvent 204 or the solvent precursor material240 introduced into the blending chamber 210 is dependent on a dopeconcentration of the nanotube dope solution 112 and the amount ofunaligned carbon nanotube material 104 fed into the blending chamber210. The dope concentration is defined as the concentration of theunaligned carbon nanotube material 104 in the nanotube solvent 204 asdetermined by weight of the unaligned carbon nanotube material 104. Forexample, the target concentration can be in the range of 2-20% by weightof the unaligned carbon nanotube material 104 while in the mixing module110 of FIG. 1, however, it is understood that the concentration canchange through the manufacturing process. For example, the dopeconcentration of the nanotube dope solution 112 at this stage ofprocessing can be lower than that of the nanotube dope solution 112during extrusion.

In another embodiment of the solid state blending step 606, theunaligned carbon nanotube material 104 can be processed in blendingchamber 202 without the addition of the solid solvent particles 206 orthe solvent precursor material 240. For example, separation elements ofthe blending elements in the blending chamber 202 can process theunaligned carbon nanotube material 104, such as separating or breakingup the unaligned carbon nanotube material 104 to increase the exposedsurface area of the unaligned carbon nanotube material 104, cool theunaligned carbon nanotube material 104, drying or aerating the unalignedcarbon nanotube material 104, or other processes to facilitatedownstream processing.

The solid state blending step 606 can allow for ingression of the solidsolvent particles 206 or the solvent precursor material 240 onto theexposed surfaces of the unaligned carbon nanotube material 104. Forexample, the separation instruments of the blending elements in theblending chamber 210 can pull apart the unaligned carbon nanotubematerial 104 to facilitate blending of the solid solvent particles 206or the solvent precursor material 240 onto the surface of the unalignedcarbon nanotube material 104. The solid state blending step 606 caninclude recirculating the unaligned carbon nanotube material 104 throughthe blending chamber 210 to constantly re-exposes the surfaces of theunaligned carbon nanotube material 104 to the solid solvent particles206 until uniform distribution of the solid solvent particles 206through the unaligned carbon nanotube material 104 is achieved. Thisdistribution of the solid solvent particles 206 is preferablyrandomized, in proportions as defined by target concentration andconsist of highly similar solvent and solute particle shapes and sizes,preferably within 10% standard variation in size along the longestparticle dimension, more preferably within 5% standard variation in sizealong the longest particle dimension, most preferably within 1% standardvariation in size along the longest particle dimension.

It has been discovered that the solid state blending step 606 providescontrolled introduction of the nanotube solvent 204 to the unalignedcarbon nanotube material 104, which is critically important tocontrolling the protonation reaction that is enthalpically favored anddiffusion-limited. The solid state blending step 606 allows fordispersion of the nanotube solvent without initiating the chemicalreaction between the nanotube solvent 204 and the unaligned carbonnanotube material 104 until uniform blending of the solid solventparticles 206 has been achieved, which provides uniform and controlleddissolution of the unaligned carbon nanotube material 104 into thenanotube solvent 204. This can maximize the dispersion of the carbonnanotube molecules 106 and optimizes alignment of the carbon nanotubemolecules 106 when producing the aligned carbon nanotube product 102.

Once blending between the solid solvent particles 206 or the solventprecursor material 240 and the unaligned carbon nanotube material 104has been completed in the solid state blending step 606, the method 600can continue to a solvent activation step 610. The solvent activationstep 610 is for activating the solid solvent particles 206, the solventprecursor material 240, or a combination thereof. In the solventactivation step 610, the solid state blend 208 can be transferred to thehomogenization unit 220 of FIG. 2.

In one embodiment the nanotube solvent 204 can be activated byliquefying the solid solvent particles 206. For example, the nanotubesolvent 204 in the cryogenic solid state can be activated by controlledheating from the solid blending temperature to a solution mixingtemperature. In general, the solution mixing temperature is below thatwhich will cause degradation of the nanotube solvent 204. In thespecific example of the nanotube solvent 204 as chlorosulfonic acid, thesolution mixing temperature can range from 25° C. to 80° C., but not toexceed the boiling temperature of 154° C. to 156° C. at atmosphericpressure, and more preferably under 80° C. In some embodiments, thesolution mixing temperature can exceed the boiling temperature ofchlorosulfonic acid when controlled under a saturated HCl atmosphere,which can prevent degradation of the chlorosulfonic acid.

Liquefying the solid solvent particles 206 activates a protonationreaction between the nanotube solvent 204 and the unaligned carbonnanotube material 104. The protonation reaction initiates the formationof a true solution as the delocalized π electron on the sp2 carbonlattice is protonated and electrostatic repulsion between protons on themolecular backbone of the carbon nanotube molecules 106 overcome theattractive van-der-Waals forces between one another, allowing the carbonnanotube molecules 106 to separate and go into solution.

In another embodiment of the solvent activation step 606, the nanotubesolvent 204 can be activated by introduction of the solvent activationagent 242 of FIG. 2 into the solid state blend 208 that includes thesolvent precursor material 240. For example, the solvent precursormaterial 240 of phosphorous pentachloride and the solvent activationagent 242 of sulfuric acid can be reacted in the enclosed mixing chamber224 at a controlled heating rate to produce the nanotube solvent 204 ofchlorosulfonic acid.

Following the solvent activation step 610, the method 600 can proceed toa homogenization step 614. The homogenization step 614 is for producingthe nanotube dope solution 112. In the homogenization step 614, thehomogenization unit 220 can mix the unaligned carbon nanotube material104 with the nanotube solvent 204 that is in the liquid state. In oneembodiment of the homogenization step 614, the nanotube solvent 204produced from liquefaction of the solid solvent particles 206 orreaction between the solvent precursor material 240 and the solventactivation agent 242 can be mixed with the unaligned carbon nanotubematerial 104. In another embodiment of the homogenization step 614, thenanotube solvent 204, such as liquid chlorosulfonic acid or asupercritical fluid, can be introduced into the homogenization unit 220for shear mixing with the unaligned carbon nanotube material 104 thathas not been blended with the solid solvent particles 206 or the solventprecursor material 240. Mixing of the unaligned carbon nanotube material104 and the nanotube solvent 204 can produce the nanotube dope solution112 that is in an optically birefringent nematic liquid crystallinephase.

In general, the nanotube dope solution 112 can be produced at aconcentration in the range of 2-20% by weight of the unaligned carbonnanotube material 104, however it is understood that the nanotube dopesolution 112 can be produced at different concentrations. For example,additional quantities can be introduced into the enclosed mixing chamberto reduce the concentration of the nanotube dope solution 112.

During the homogenization step 614, the nanotube dope solution 112 canbe evaluated to determine the degree of protonation between the nanotubesolvent 204 and the unaligned carbon nanotube material 104. For example,the measurement devices of the homogenization unit 220, can monitor theproperties or characteristics of the nanotube dope solution 112, such aswavelength shifts and viscosity, to determine whether adequatehomogenization of the nanotube dope solution 112 has been reached. Inone specific example, the wavelength shift associated with theprotonation of the sp2 carbon structure can be measured by themeasurement devices, such as the inline Raman spectrometer. In anotherspecific example, the viscoelasticity and optical birefringence of thenanotube dope solution 112 can be measured to determine the degree ofliquid crystal formation by the measurement devices, such as mechanical,optical, or other non-contact rheometers. The nanotube dope solution 112can be recirculated through the homogenization unit 220 via the flowrecirculation loop 226 of FIG. 2 until satisfactory protonation isachieved.

Both the solvent activation step 610 and the homogenization step 614 canbe performed in the homogenization unit 220. The homogenization unit 220can evacuate by-products produced from the protonation reaction, such ashydrochloric acid gas, during the solvent activation step 610, thehomogenization step 614, or a combination thereof.

The method 600 can optionally include a concentration adjustment step616, as indicated by the dashed arrows and lines. The concentrationadjustment step 616 is for adjusting the concentration of the nanotubedope solution 112. In some embodiments, the unaligned carbon nanotubematerial 104 and the nanotube solvent 204 can be charged into theblending unit 202 in such a proportion as to target a concentration thatis lower than that of the target concentration for the nanotube dopesolution 112 during formation of the nanotube proto-product 122 of FIG.1 to reduce strain on the various units and elements in the mixingmodule 110. The final target concentration for the nanotube dopesolution 112 can be achieved by feeding the reduced concentration formof the nanotube dope solution 112 into the concentration adjustment unit230 of FIG. 2, which can evaporating the nanotube solvent 204 withoutdegradation.

In the concentration adjustment step 616, the concentration adjustmentunit 230 can be operated under temperature and atmospheric conditions toprevent degradation of the nanotube solvent 204. For example, theconcentration adjustment unit 230 can be operated to provide an HCl gasenriched or saturated atmosphere that can be co-fluxed or co-flowed withnanotube solvent 204 that has evaporated from the nanotube dope solution112. In general, the concentration adjustment unit 230 can be operatedat pressures of 30 to 35 mm Hg or 0.039 to 0.046 atmospheres andtemperatures ranging from 85 to 90° C.

Once sufficient mixing and target concentration of the nanotube dopesolution 112 has been achieved in the homogenization step 614, thenanotube dope solution 112 can undergo a passive transfer mixing step618. In the passive transfer mixing step 618, the nanotube dope solution112 can undergo additional passive mixing through the static mixingelements of FIG. 3 along the fluid path during transfer from the mixingmodule 110 to the extrusion module 120. The purpose of passive transfermixing step 618 is to create a sustained turbulent flow regime for thenanotube dope solution 112. Turbulent flow of the nanotube dope solution112 provides continued mixing while also providing controlled heattransfer within the nanotube dope solution 112, such as through heatexchange fluid recirculation inside and outside the static mixingelements.

The method 600 can include a filtration step 620 to remove theimpurities from the nanotube dope solution 112. For example, it ispossible that in some cases, despite the use the unaligned carbonnanotube material 104 that has been purified, impurities, such asmultiple undispersed, undesired particles, insufficiently pure instancesof the unaligned carbon nanotube material 104, residual catalystparticles, and residual amorphous or sp3 carbon, or a combinationthereof can be present in the nanotube dope solution 112. The impuritiescan be removed from the nanotube dope solution 112 in the filtrationstep 620 by passing the nanotube dope solution 112 through thefiltration unit 302 of FIG. 3. As an example, filtration of theimpurities can be achieved by flow through the filtration elements 304of FIG. 3, such as the coarse filtration element 330, the finefiltration element 332, or a combination thereof. The inclusion of thecoarse filtration element 330 or the fine filtration element 332 candepend on initial purity of the unaligned carbon nanotube material 104.

Following the filtration step 620, the process flow can continue to afractionation step 624. The fractionation step 624 is for separation ofthe carbon nanotube molecules 106 in the nanotube dope solution 112based on the aspect ratio of the carbon nanotube molecules 106. Ingeneral, the nanotube dope solution 112 can include a mixture of thecarbon nanotube molecules 106 having a wide range of aspect ratios. Inthe fractionation step 624, the nanotube dope solution 112 can besubjected to shear flow in the fractionation pathway 306 of theextrusion flow manifold 316, both of FIG. 3. Under sufficiently highshear, it is expected that the nanotube dope solution 112 will phaseseparate into the highly crystalline phase 340 of FIG. 3, which iscomprised primarily of the carbon nanotube molecules 106 having thehighest aspect ratio in the nanotube dope solution 112, and theconcentrated isotropic phase 342 of FIG. 3, which is comprised primarilyof the carbon nanotube molecules 106 having the lowest aspect ratio inthe nanotube dope solution 112.

In the fractionation step 624, the extrusion flow manifold 316 canseparate and redirect the concentrated isotropic phase 342 from thehighly crystalline phase 340 as processing waste or low-grade material.The highly crystalline phase can be allowed to proceed towards theextrusion assembly 310 of FIG. 3. During transfer to the extrusionassembly 310, additional homogenization and temperature control can beimparted on the nanotube dope solution 112 through a static mixer or anassembly of static mixers of the extrusion flow manifold 316.

The process continues from the fractionation step 624 to an extrusionstep 626. In the extrusion step 626, the nanotube dope solution 112 isprocessed to impart the initial form and alignment for the alignedcarbon nanotube product 102, which is the carbon nanotube proto-product122. For example, the nanotube dope solution 112 can flow through theone of the various possible configurations of the extrusion assembly 310of FIG. 3 to produce the carbon nanotube proto-product 122 of aparticular form, shape, or dimension, such as the fiber, filament, orfilm. In some embodiments, the liquid crystalline domains of thenanotube dope solution 112 can be twisted, rotated, or a combinationthereof during the extrusion step 626 to confer extra strength to thecarbon nanotube proto-product 122 once the domains are solidified in thetwisted configuration, a spiral configuration, a helical configuration,or a combination thereof.

The extrusion step 626 can optionally include a flow vibration step 628,as indicated by the dashed arrows and lines. The flow vibration step 628is for facilitating the flow of the nanotube dope solution 112 throughthe extrusion die 314. For example, in the flow vibration step 628, theextrusion die 314 can be vibrated by the vibratory apparatus to aid flowof the nanotube dope solution 112 through the extrusion die 314 bydisturbing undesired elastic turbulence immediately prior to the outletof the extrusion die 314, improving flow stability by reducingundesirable frictional and shearing effects along flow surfaces, or acombination thereof.

Following the extrusion step 626, the carbon nanotube proto-product 122can continue to an alignment and solidification step 630. At this stage,the carbon nanotube proto-product 112 can be produced having acomposition that is primarily of the nanotube solvent 204, as measuredby volume or weight fraction. In the alignment and solidification step630, the carbon nanotube proto-product 122 is processed in a combinationof drawing and alignment processes to form the aligned carbon nanotubeproduct 102. As an example, the alignment and solidification step 630can include an initial alignment step 632, an irradiative coagulationstep 634, an intermediate alignment step 636, a chemical coagulationstep 638, a solid state alignment step 640, or a combination thereof.

The initial alignment step 632 can follow production of the carbonnanotube proto-product 122 in order to impart an initial alignment tothe carbon nanotube proto-product 122. For example, in the initialalignment step 632, the carbon nanotube proto-product 122 can be drawnunder tension by the initial alignment unit 402 of FIG. 4 to align ofthe carbon nanotube molecules 106 in the carbon nanotube proto-product122 by, for example, operating the initial alignment unit 402 at a drawrate that is a speed faster than the flow speed for the carbon nanotubeproto-product 122 as it exits the extrusion die 314 of FIG. 4. As anexample, the draw rate during the initial alignment step 632 can be setto produce an alignment corresponding to a Herman orientation factor ofpreferably at least 0.8, more preferably at least 0.9, and mostpreferably at least 0.95 as measured by in-line X-ray or neutronscattering techniques.

The irradiative coagulation step 634 can follow the initial alignmentstep 632. The irradiative coagulation step 634 is for initiatingsolidification through exposing the carbon nanotube proto-product 122 toradiation from the radiation source 406 of FIG. 4. In the irradiativecoagulation step 634, the carbon nanotube proto-product 122 is exposedto radiation, such as infrared radiation, from the radiation source 406at a wavelength that minimizes absorption by the nanotube solvent 204and maximizes absorption of the radiation by carbon nanotube molecules106 of the carbon nanotube proto-product 122. As an example, theirradiative coagulation unit 404 can produce incident irradiation at awavelength in the range of 1 to 130 μm. The irradiative coagulation step634 can include pulsing of the radiation source 406 to prevent localizedheating effects in and along the carbon nanotube proto-product 122. Theirradiative coagulation step 634 can provide convective heat transferthrough, for example, evacuation of the nanotube solvent 204 from theirradiative coagulation unit 404 and impose gas flow in the atmospheresurrounding the carbon nanotube proto-product 122, as well as aid inconveying the carbon nanotube proto-product 122.

The intermediate alignment step 636 can follow the irradiativecoagulation step 634. The intermediate alignment step 636 is forimparting alignment to the carbon nanotube proto-product 122. In theintermediate alignment step 636, the carbon nanotube proto-product 122is in a partially solidified state and can be drawn under tension by theintermediate alignment unit 408 of FIG. 4 to align of the carbonnanotube molecules 106 in the carbon nanotube proto-product 122 by, forexample, operating the intermediate alignment unit 408 at a speed fasterthan the flow speed for the carbon nanotube proto-product 122 as itexits the extrusion die 314. The rate and tension under which the carbonnanotube proto-product 122 is drawn by the intermediate alignment unit408 can be the same as, greater than, or less than that of the initialalignment unit 402 in the initial alignment step 632.

The chemical coagulation step 638 can follow the intermediate alignmentstep 636. In the chemical coagulation step 638, the carbon nanotubeproto-product 122 is solidified through exposure to the chemicalcoagulant 412. For example, the carbon nanotube proto-product 122 can beexposed to the chemical coagulant 412 in the chemical coagulation unit410 of FIG. 4. As specific examples, exposing the carbon nanotubeproto-product 122 to the chemical coagulant 412 can include spraying,bath immersion, passing through a fluid film that is continuouslyrenewed, or a combination thereof. The chemical coagulation step 638 canprovide a homogeneous rate of coagulation along the cross-section of thecarbon nanotube proto-product 122. Further, the chemical coagulationstep 638 can include atmospheric control of the chemical coagulationunit 410 and convective heat transfer through evacuation of the volatilesubstances and imposed gas flow on the atmosphere surrounding the carbonnanotube proto-product 122, as well as aid in conveying the carbonnanotube proto-product 122.

The solid state alignment step 640 can follow the irradiativecoagulation step 634, the chemical coagulation step 638, or acombination thereof. The solid state alignment step 640 is for solidstate alignment of the carbon nanotube proto-product 122. In the solidstate alignment step 640, solidification of the carbon nanotubeproto-product 122 is nearly complete and can be drawn under tension bythe solid state alignment unit 414 of FIG. 4 to impose the final degreeof alignment to the carbon nanotube molecules 106 in the carbon nanotubeproto-product 122 in order to form the aligned carbon nanotube product102, set the final dimensions of the aligned carbon nanotube product102, or a combination thereof. As an example, the solid state alignmentunit 414 can be operated at a speed faster than the flow speed for thecarbon nanotube proto-product 122 as it exits the extrusion die 314. Therate and tension under which the carbon nanotube proto-product 122 isdrawn by the solid state alignment unit 414 can be the same as, greaterthan, or less than that of the initial alignment unit 402 in the initialalignment step 632, the intermediate alignment unit 408 in theintermediate alignment step 404, or a combination thereof. The alignedcarbon nanotube product 102 can be wound on a creel for storagefollowing the solid state alignment step 640.

Following production of the aligned carbon nanotube product 102, themethod 600 can continue to a purification step 650. In the purificationstep 650, the aligned carbon nanotube product 102 can undergo acombination of one or more processes to remove residual amounts of thenanotube solvent 204, residual amounts of the chemical coagulant 412,any other undesired residual particle on the aligned carbon nanotubeproduct 102, or a combination thereof. As an example, the purificationstep 650 can include an aqueous wash step 652, a thermal annealing step654, a chemical wash step 656, or a combination thereof. Thepurification step 650 represents one embodiment for purifying thealigned carbon nanotube product 102, although it is understood thatadditional steps and other permutation or arrangements can beimplemented.

The aqueous wash step 652 is for removing residual traces of thenanotube solvent from the aligned carbon nanotube product 102. In theaqueous wash step 652, the aligned carbon nanotube product 102 can beexposed to an aqueous solution, such as distilled or purified water, inthe solvent removal unit 504 of FIG. 5 to remove residual amounts of thenanotube solvent 204. For example, exposing the aligned carbon nanotubeproduct 102 to the aqueous solution can include can include spraying,bath immersion, passing through a fluid film which that is continuouslyrenewed, or a combination thereof. During the aqueous wash step 652, theaqueous solution can be maintained at a temperature in the range of 60°C. to 80° C.

The thermal annealing step 654 is for removing residual traces of thechemical coagulant 412 from the aligned carbon nanotube product 102. Thethermal annealing step 654 can be carried out in the thermal annealingunit 506 of FIG. 5 in a heated and controlled environment. For example,in the thermal annealing step 654, the aligned carbon nanotube product102 can be heated to a volatilization temperature in the thermalannealing unit 506 to remove remaining amounts of the chemical coagulant412. As a specific example, the volatilization temperature can be in arange of 120° C. to 250° C.

The chemical wash step 656 is for removing by-products from reactionsbetween the nanotube coagulant and the nanotube solvent 204. Forexample, in the chemical wash step 656, the aligned carbon nanotubeproduct 102 can be exposed to the chemical wash solution of FIG. 5 inthe chemical wash unit 508 of FIG. 5. As specific examples, exposing thealigned carbon nanotube product 102 to the chemical wash solution caninclude spraying, bath immersion, passing through a fluid film that iscontinuously renewed, or a combination thereof. The chemical washsolution can be a non-carbon nanotube solvent that can remove anyundesired by-products of reaction between the nanotube solvent 204 thechemical coagulant 412.

The method 600 can include one or more optional steps to modify thealigned carbon nanotube product 102. For example, the method 600 canoptionally include a functionalization step 660, a coating step 670, adoping step 680, a product integration step 690, or a combinationthereof.

The functionalization step 660 is for modifying the molecular structureof the aligned carbon nanotube product 102. For example, thefunctionalization step 660 can include a vulcanization process, whichcan cross-link the carbon nanotube molecules 106 in the aligned carbonnanotube product 102. As a specific example, in the vulcanizationprocess, sulfur groups can be attached to the molecular backbone of thecarbon nanotube molecules 106 by doping the aligned carbon nanotubeproduct 102 with polystyrene sulfonate (PEDOT), which can then annealedat 800° C. in an oxygen-free atmosphere in the oven of thefunctionalization unit 512 of FIG. 5. Once a set number of the sulfurgroups have been attached to the molecular backbones of the carbonnanotube molecules 106, a standard vulcanization reaction to cross-linkthe sulfur groups can be performed.

The functionalization step 660 that includes vulcanization can increasethe mechanical properties of the aligned carbon nanotube product 102,but can reduce electrical conductivity of the aligned carbon nanotubeproduct 102. Similarly, other forms of chemical functionalization arepossible, but can also come at the expense of a reduction in electricalconductivity.

The coating step 670 is for coating the surface of the aligned carbonnanotube product 102. In the coating step 670, a layer of coatingsubstance can be applied to the surface of the aligned carbon nanotubeproduct 102. In one example, the coating substance can be applied to thealigned carbon nanotube product 102 through a mechanical process, suchas dip-coating, roll-to-roll coating, slide-coating, immersion coating,or other available mechanical coating technologies, as determined by thecoating material. In another example, the coating substance can beapplied to the aligned carbon nanotube product 102 through anelectrolytic process, including immersion of the to the aligned carbonnanotube product 102 in an electrolytic bath containing an ioniccompound in an aqueous dispersion at a suitable zeta potential level. Ina further example, the coating substance can be applied to the alignedcarbon nanotube product 102 through electrostatic coating of chargedsolid particles or gas-phase deposition.

The doping step 680 is for non-covalent chemical functionalization ofthe aligned carbon nanotube product 102. For example, in the doping step680, the aligned carbon nanotube product 102 can undergo p-type dopingwith p-type donors, such as iodine or sulfuric acid. In oneimplementation, the doping step 680 can include gas phase doping, suchas with iodine doping. In another implementation, the doping step 680can include liquid phase doping, such as with acid doping. Following thedoping step 680, the aligned carbon nanotube product 102 can be coatedin the coating step 670 to ensure dopant stability over time.

The product integration step 690 is for integration of the alignedcarbon nanotube product 102 into devices, components, or structures. Forexample, the aligned carbon nanotube product 102 produced following thealignment and solidification step 630, the purification step 650, thefunctionalization step 660, the coating step 670, the doping step 680,or a combination thereof can be integrated into a variety of structures,devices, or components through inline or semi-inline processes. Examplesof structures can include ropes, yarns, woven fabrics, foams, resinpre-impregnated tapes or fabrics, chopped fiber filler material,laminated films made from the aligned carbon nanotube product 102 or incombination with other materials, such as Kevlar, fiberglass, or metals.In the product integration step 690, the aligned carbon nanotube product102 can be twisted, braided, woven, pressed, rolled, bonded, laminated,coated, cut or a combination thereof to form the various structures.

Examples of integration of the aligned carbon nanotube product 102 indevices or components can include wire antennas, patch antennas, coiltransformers, coaxial cables. In the example of producing the wireantennas, coated or uncoated forms of the aligned carbon nanotubeproduct 102 can be woven into single or multi-filament threads, yarns,or rope which can be cut to length as determined by a specified resonantfrequency.

In the example of producing the patch antenna, the cutting the coated oruncoated film form of the aligned carbon nanotube product 102 can be cutto specified antenna geometry. The resulting form can be deposited ontoa dielectric substrate, which can be co-extruded using melt or solutionprocessing.

In the example of producing the coil transformer, the aligned carbonnanotube product 102 can be woven into a thread, yard, or rope, whichcan be wound around a ferritic or magnetic core to form a coil. Thenumber of windings can be determined by the inductance that is to beachieved by the coil.

In the example of producing the coaxial cables, the carbon nanotubeproto-product 104 can be co-extruded with a dielectric material. Oncethe carbon nanotube proto-product 104 has been solidified, thedielectric material can be solidified as an encapsulation with thealigned carbon nanotube product 102 as the inner conductor.

These and other valuable aspects of an embodiment of the presentinvention consequently further the state of the technology to at leastthe next level.

While the invention has been described in conjunction with a specificbest mode, it is to be understood that many alternatives, modifications,and variations will be apparent to those skilled in the art in light ofthe aforegoing description. Accordingly, it is intended to embrace allsuch alternatives, modifications, and variations that fall within thescope of the included claims. All matters set forth herein or shown inthe accompanying drawings are to be interpreted in an illustrative andnon-limiting sense.

1-18. (canceled)
 19. A method of manufacturing a carbon nanotubeproduct, comprising: mixing an unaligned carbon nanotube materialcomprising carbon nanotube molecules with a solvent precursor material;activating a nanotube solvent by reacting the solvent precursor materialwith a solvent activation agent; producing a nanotube dope solution bymixing the nanotube solvent and the unaligned carbon nanotube material;forming a carbon nanotube proto-product by extruding the nanotube dopesolution thereby imparting alignment to carbon nanotube molecules of thecarbon nanotube proto-product; and forming an aligned carbon nanotubeproduct by solidifying the carbon nanotube proto-product.
 20. A carbonnanotube product manufacturing system, comprising: a blending unitconfigured to blend an unaligned carbon nanotube material with solidsolvent particles; a homogenization unit configured to: activate ananotube solvent by liquefying the solid solvent particles; and mix thenanotube solvent and the unaligned carbon nanotube material to produce ananotube dope solution; an extrusion assembly configured to extrude thenanotube dope solution as a carbon nanotube proto-product; and asolidification module configured to solidify the carbon nanotubeproto-product as an aligned carbon nanotube product.
 21. The method ofclaim 19, wherein forming the carbon nanotube proto-product includesextruding the nanotube dope solution as a nanotube filament.
 22. Themethod of claim 19, wherein forming the carbon nanotube proto-productincludes extruding the nanotube dope solution as a nanotube film
 23. Themethod of claim 19, further comprising cryogenically freezing thenanotube solvent to form the solid solvent particles prior to blendingwith the unaligned carbon nanotube material.
 24. The method of claim 19,wherein the nanotube solvent is chlorosulfonic acid.
 25. The method ofclaim 19, further comprising, prior to extruding the nanotube dopesolution, adding an additional amount of the nanotube solvent in aliquid state to the nanotube dope solution.
 26. The method of claim 19,further comprising removing an amount of the nanotube solvent from thenanotube dope solution through evaporation under co-flow with gaseoushydrochloric acid to prevent degradation of the nanotube solvent. 27.The method of claim 19, wherein producing the nanotube dope solutionincludes producing the nanotube dope solution at a concentration between2% and 20% by weight of the unaligned carbon nanotube material.
 28. Themethod of claim 19, further comprising fractionating the nanotube dopesolution to remove carbon nanotube molecules of the lowest aspect ratioin the nanotube dope solution.
 29. The method of claim 19, whereinforming the aligned carbon nanotube product includes solidifying thecarbon nanotube proto-product by exposing the carbon nanotubeproto-product to an infrared radiation source.
 30. The method of claim19, wherein forming the aligned carbon nanotube product includessolidifying the carbon nanotube proto-product by exposing the carbonnanotube proto-product to a chemical coagulant.
 31. The method of claim19, further comprising drawing the carbon nanotube proto-product toimpart further alignment of carbon nanotube molecules in the carbonnanotube proto-product.
 32. The method of claim 19, further comprisingthermally annealing the aligned carbon nanotube product to remove anamount of the chemical coagulant from the aligned carbon nanotubeproduct.
 33. The method of claim 19, further comprising doping thealigned carbon nanotube product.
 34. The method of claim 19, furthercomprising coating the surface of the aligned carbon nanotube product.35. The method of claim 19, further comprising integrating of thealigned carbon nanotube product with additional instances of the alignedcarbon nanotube product, other materials, or a combination thereof, toproduce integrated structures selected from yarns, threads, wovenfabrics, laminated films, tape, foam, composite pre-preimpregnatedmaterials, and discrete length chopped fiber material.
 36. The method ofclaim 19, further comprising integrating of the aligned carbon nanotubeproduct with additional instances of the aligned carbon nanotubeproduct, other materials, or a combination thereof to produce acomponent selected from wire antennas, patch antennas, coiltransformers, and coaxial cables.